Process for preparing a crystalline aluminosilicate

ABSTRACT

Crystalline aluminosilicates, a process for the production thereof and uses therefor are disclosed. The crystalline aluminosilicates are of new crystalline structure, which, as determined after calcination in the air at 550° C., have a composition represented by the general formula (I): 
     
         pM.sub.2/n O.Al.sub.2 O.sub.3.qSiO.sub.2 
    
     (the symbols are as defined in the appended claims) and give a principal X-ray diffraction pattern as shown in Table 1. They are used as catalysts for the conversion of synthesis gas or oxygen-containing organic compounds such as alcohol, ether into hydrocarbons.

BACKGROUND OF THE INVENTION

The present invention relates to: (1) novel crystalline aluminosilicate(hereinafter referred to as "crystalline aluminosilicate (ISI-6)"), (2)a process for preparing said crystalline aluminosilicate (ISI-6), (3) aprocess for producing hydrocarbons from oxygen-containing compounds withcrystalline aluminosilicate (ISI-6) as a catalyst, and (4) a process forproducing hydrocarbons from synthesis gas in the presence of a catalystcomprising crystalline aluminosilicate (ISI-6) and metals having anability to reduce carbon monoxide.

A number of crystalline aluminosilicates, natural or synthetic, haveheretofore been known and various processes have been proposed toprepare such crystalline aluminosilicates. These crystallinealuminosilicates are usually prepared by subjecting an aqueous mixtureconsisting of a silica source, an alumina source and an alkali metalsource to a hydrothermal reaction.

A process for preparing crystalline aluminosilicate zeolite having aspecial crystal structure by adding organic compounds exemplified bytetrapropylammonium bromide to the above described aqueous mixture hasrecently been developed. For example, Japanese Patent ApplicationLaid-Open Nos. 43800/1977 and 134571/1981 disclose that addition ofalcohols results in the preparation of ZMS-5 type zeolite and Zeta 1 or3 type zeolite. U.S. Pat. No. 4,046,859, No. 4,107,195 and No. 4,146,584disclose that addition of nitrogen-containing compounds results in theformation of ZSM-21 type of ZSM-35 type zeolite. Furthermore, U.S. Pat.No. 4,251,499 describes that ferrierite is prepared by using piperidineor its derivatives.

SUMMARY OF THE INVENTION

As a result of extensive investigations to develop aluminosilicate ofnovel composition and crystal structure, it has been found that novelcrystalline aluminosilicate having a high silica content can be preparedby adding pyridines and oxygen-containing organic compounds, orpyridines and nitrogen-containing organic compounds except pyridines toan aqueous mixture containing a silica source, an alumina source, analkali metal source, etc. in a predetermined ratio.

This novel crystalline aluminosilicate is called herein "crystallinealuminosilicate (ISI-6)".

The present invention relates to:

(1) a crystalline aluminosilicate having a composition, as determinedafter being calcined in air at 550° C. and expressed in molar ratio,represented by the formula (I):

    pM.sub.2/n O.Al.sub.2 O.sub.3.qSiO.sub.2                   (I)

(wherein M is at least one element selected from alkali metals, alkalineearth metals, and a hydrogen atom, n is a valency of M, and p and q arechosen within the ranges of 0.05≦p≦3.0 and 5≦q≦500) and further having aprincipal X-ray diffraction pattern shown in Table 1;

(2) a process for preparing a crystalline aluminosilicate having acomposition, as determined after being calcined in air at 550° C. andexpressed in molar ratio, represented by the formula (I) as describedabove and further having a principal X-ray diffraction pattern shown inTable 1, which comprises reacting an aqueous mixture containing (a) asilica source, (b) an alumina source, (c) an alkali metal and/oralkaline earth metal source, (d) a pyridine or derivative thereof, and(e) a component selected from the group consisting of (i) anoxygen-containing organic compound and (ii) a nitrogen-containingorganic compound other than a pyridine or derivative thereof in thefollowing molar ratios:

silica (SiO₂)/alumina (Al₂ O₃)≧5

a pyridine or derivative thereof/silica=0.01 to 100

component (e)/silica=0.01 to 100

hydroxyl ion/silica=0.001 to 0.5 (excluding hydroxyl ions resulting fromorganic bases)

water/silica=5 to 1,000

alkali metal and/or alkaline earth metal/silica=0.01 to 3

at a temperature ranging between 100° and 300° C. till the crystallinealuminosilicate is formed;

(3) a process for producing hydrocarbons which comprises bringingoxygen-containing compounds into contact with the crystallinealuminosilicate as described in (1) above; and

(4) a process for producing hydrocarbons which comprises bringingsynthesis gas into contact with a catalyst comprising (A) a metal ormetal compound having an ability to reduce carbon monoxide and (B) thecrystalline aluminosilicate as described in (1) above.

The above numbered inventions are herein referred to as Inventions (1),(2), (3) and (4), respectively.

                  TABLE 1                                                         ______________________________________                                        Lattice Spacing (Å)                                                                      Relative Intensity (%)                                         ______________________________________                                        9.44 ± 0.2  100                                                            7.07 ± 0.2  4-40                                                           6.92 ± 0.15 4-30                                                           6.59 ± 0.15 4-30                                                           5.74 ± 0.15 4-30                                                           3.97 ± 0.1  20-100                                                         3.92 ± 0.1  20-70                                                          3.83 ± 0.1  5-50                                                           3.77 ± 0.1  5-50                                                           3.64 ± 0.07 20-100                                                         3.53 ± 0.07 20-100                                                         3.46 ± 0.07 20-80                                                          3.36 ± 0.07 4-20                                                           3.30 ± 0.07 4-20                                                           3.12 ± 0.07 4-30                                                           3.04 ± 0.07 4-20                                                           Irradiation: Cu--K.sub.α                                                               Wavelength: 1.5418 Å                                       ______________________________________                                    

BRIEF DESCRIPTION OF THE DRAWING

The FIGURE is an X-ray diffraction pattern of the crystallinealuminosilicate prepared in Example 1. The symbol θ represents aglancing angle.

DETAILED DESCRIPTION OF THE INVENTION

Invention (2) will hereinafter be explained in detail.

An aqueous mixture is prepared by adding (a) a silica source, (b) analumina source, (c) an alkali metal and/or alkaline earth metal source,(d) a pyridine or its derivative, and (e) a component selected from thegroup consisting of (i) an oxygen-containing organic compound and (ii) anitrogen-containing organic compound other than component (d) to waterand then is allowed to react at elevated temperatures.

The silica source (a) is not subject to any special limitation; forexample, powdered silica, silicic acid, colloidal silica, and dissolvedsilica can be used. Examples of such dissolved silicas include waterglass containing 1 to 5 moles of SiO₂ per mole of Na₂ O or K₂ O,silicate, and alkali metal silicate.

Various compounds can be used as the alumina source (b), includingaluminum sulfate, sodium aluminate, colloidal alumina, and alumina.

The ratio of silica to alumina in the aqueous mixture can be determinedappropriately. The molar ratio of silica (SiO₂) to alumina (Al₂ O₃) isat least 5:1, preferably at least 10:1, and most preferably 15:1 to1,000:1

As the alkali metal and/or alkaline earth metal source (c), variouscompounds can be used. The alkali metals and the alkaline earth metalsinclude sodium, potassium, lithium, magnesium and barium. The preferredmetals are sodium, potassium and lithium. Examples of the alkali metalsource include sodium hydroxide and potassium hydroxide. In addition,sodium silicate and sodium aluminate can be used. These compounds serveas both the silica or alumina source and the alkali metal source.Examples of the alkaline earth metal source include calcium nitrate andcalcium chloride.

The molar ratio of alkali metal and/or alkaline earth metal to silica isnot critical and can be determined appropriately depending on othervarious conditions. It is usually 0.01:1 to 3:1 and particularlypreferably 0.1:1 to 1:1.

The pyridine or its derivative (d) as used herein act mainly as acrystallization agent. Examples of pyridine derivatives includeprydinium chloride, methylpyridine, dimethylpyridine, ethylpyridine,trimethylpyridine, and ethylmethylpyridine. The amount of the pyridineor its derivative being used is usually determined so that the molarratio of pyridine or its derivative (component (d) to silica is 0.01:1to 100:1 and preferably 0.05:1 to 10:1.

The oxygen-containing organic compound (e) plays an important role incombination with the component (d) in the formation of the desiredcrystal structure during the process of preparation of the crystallinealuminosilicate. Suitable examples of the oxygen-containing organiccompounds (e) include alcohols, such as methanol, ethanol, propanol,n-butanol, and isopropanol, glycols, such as ethylene glycol andpropylene glycol, and ethers, such as dimethyl ether and diethyl ether.Particularly preferred are n-propanol, ethylene glycol, and propanediol. In the Invention (2), as the component (e), a nitrogen-containingorganic compound other than a pyridine or derivative thereof(hereinafter referred to merely as the "nitrogen-containing organiccompound") can be used in place of the oxygen-containing organiccompound. Suitable examples of the nitrogen-containing organic compoundsinclude amines such as isopropylamine and morpholine, diamines such asethylenediamine, propylenediamine, and phenylenediamine, andaminoalcohols such as monoethanolamine, monopropanolamine anddiethanolamine. Of these compounds, morpholine, ethylenediamine,monoethanolamine, and monopropanolamine are preferred. The amount of thecomponent (e) used is determined so that the molar ratio of thecomponent (e) to silica is 0.01:1 to 100:1 and preferably 0.05:1 to10:1.

These components (a), (b), (c), (d) and (e) are added to water in theabove described molar ratios to prepare an aqueous mixture which is thensubjected to a hydrothermal reaction. The molar ratio of hydroxyl ionsto silica in the aqueous mixture is 0.001 to 0.5 and preferably 0.005 to0.2. In determining this molar ratio, hydroxyl ions resulting fromorganic bases such as pyridines are excluded.

In the hydrothermal reaction of the aqueous mixture, it is sufficientfor the aqueous mixture to be heated under such conditions, temperatureand time, as to form the crystalline aluminosilicate (ISI-6). Forexample, the aqueous mixture is reacted at autogenous-pressure or underpressure at a temperature of 80° to 300° C., preferably 120° to 200° C.for a period of 5 hours to 10 days, preferably 8 hours to 7 days. Thereaction is usually performed while stirring the aqueous mixture. Theatmosphere may be replaced by inert gas, if necessary. The pH of theaqueous mixture is adjusted to neutral or alkaline.

It is required for the reaction to be performed always in the presenceof the component (d) and the component (e). In the absence of thecomponent (d) or the component (e), the desired crystallinealuminosilicate cannot be obtained.

The order in which the above described components are added in thereaction is not critical. According to a preferred embodiment, thesilica source (a), the alumina source (b) and the alkali metal and/oralkaline earth metal source (c) are first added to water and then amixture of the component (d) and the component (e) is added thereto.

After the reaction is completed, the reaction mass is washed with water,dried at about 120° C. and further calcined in air at 550° C., whereuponcrystalline aluminosilicate (ISI-6) having a composition represented bythe formula (I) as described above and a principal X-ray diffractionpattern shown in Table 1.

The principal X-ray diffraction pattern of crystalline aluminosilicate(ISI-6) of the invention is, as described above, shown in Table 1.Relative intensities at lattice spacings not shown in Table 1 are notcritical. In particular, however, an X-ray diffraction pattern as shownin Table 2 is preferred.

                  TABLE 2                                                         ______________________________________                                        Lattice Spacing (Å)                                                                      Relative Intensity (%)                                         ______________________________________                                        11.33 ± 0.2 0-5                                                            9.44 ± 0.2  100                                                            7.07 ± 0.2  4-40                                                           6.92 ± 0.15 4-30                                                           6.59 ± 0.15 4-30                                                           5.74 ± 0.15 4-30                                                           5.40 ± 0.15 0-5                                                            4.94 ± 0.15 0-5                                                            4.81 ± 0.15 0-5                                                            4.71 ± 0.15 0-20                                                           3.97 ± 0.1  20-100                                                         3.92 ± 0.1  20-70                                                          3.83 ± 0.1  5-50                                                           3.77 ± 0.1  5-50                                                           3.64 ± 0.07 20-100                                                         3.53 ± 0.07 20-100                                                         3.46 ± 0.07 20-80                                                          3.36 ± 0.07 4-20                                                           3.30 ± 0.07 4-20                                                           3.12 ± 0.07 4-30                                                           3.04 ± 0.07 4-20                                                           2.94 ± 0.07 0-5                                                            2.88 ± 0.07 0-5                                                            2.83 ± 0.07 0-5                                                            2.70 ± 0.05 0-5                                                            2.64 ± 0.05 0-5                                                            2.60 ± 0.05 0-5                                                            2.58 ± 0.05 0-5                                                            Irradiation: Cu--K.sub.α                                                               Wavelength: 1.5418 Å                                       ______________________________________                                    

The relative intensity was determined with the intensity at the latticespacing of 9.44±0.2 Å as 100%.

Crystalline aluminosilicate (ISI-6) is silicate having a novel crystalstructure and thus can be used in various reactions as a solid acidcatalyst or as a catalyst support. In particular, it can be usedeffectively as a catalyst for use in the production of hydrocarbons.

Thus, next, Invention (3) will hereinafter be explained in detail.

Liquid hydrocarbons used as a gasoline fuel have heretofore beenproduced from petroleum. In view of exhaustion of petroleum which ispredicted to occur in the future, production of gasoline from feedstocksother than petroleum, such as coal and biomass, is now underinvestigation. U.S. Pat. No. 4,039,600, for example, discloses a processfor producing hydrocarbons by passing methanol or dimethyl ether overZSM-5 type aluminosilicate. These conventional methods, however, havedisadvantages in that the yield of the desired liquid hydrocarbon is notsatisfactorily high.

As a result of extensive investigations to develop a process forproducing hydrocarbons from oxygen-containing compounds derived fromcoal, biomass and other various materials in a simplified manner andfurthermore in a high conversion over long periods of time, it has beenfound that hydrocarbons can be produced with high efficiency by the useof the crystalline aluminosilicate (ISI-6) as a catalyst.

Invention (3) is concerned with a process for producing hydrocarbonsfrom oxygen-containing compounds by bringing said oxygen-containingcompounds into contact with crystalline aluminosilicate (ISI-6) as acatalyst.

Any oxygen-containing compounds can be used in Invention (3). Theseoxygen-containing compounds have from 1 to 4 carbon atoms and includealcohols, ethers, aldehydes, and carboxylic acids. Suitable examples aremethanol, ethanol, propanol, butanol, dimethyl ether, diethyl ether,acetoaldehyde, propylaldehyde, acetic acid, and propionic acid. Anespecially preferred one is methanol.

The catalyst used in Invention (3) is, as described above, crystallinealuminosilicate (ISI-6) having a composition, as determined after beingcalcined in air at 550° C. and expressed in molar ratio, represented bythe formula (I) and a principal X-ray diffraction pattern shown inTable 1. This crystalline aluminosilicate is usually used as a proton(H) type silicate, a sodium (Na) type silicate, a potassium (K) typesilicate, a lithium (Li) type silicate or a magnesium (Mg) typesilicate. The aluminosilicate can be used also as metal ion (forexample, Pt, Pd, Ni) exchange type silicate which is prepared by ionexchanging alkali metals, such as sodium, or alkaline earth metalscontained therein by various techniques. A particularly suitable exampleis crystalline aluminosilicate having an X-ray diffraction pattern shownin Table 2.

Contacting the oxygen-containing compound with the above describedcrystalline aluminosilicate is performed at atmospheric pressure orunder pressure at a temperature of 250° to 600° C., preferably 300° to500° C. at a weight hourly space velocity (WHSV) of 0.1 to 50 per hour,preferably 0.5 to 10 per hour.

In accordance with the process of Invention (3), hydrocarbons,especially olefins having from 2 to 4 carbon atoms can be obtained inhigh yields from oxygen-containing compounds derived from feedstocksother than petroleum, such as coal and biomass. Thus this can beutilized effectively in the production of feed materials for use inchemical industry.

Next, Invention (4) will hereinafter be explained in detail.

Olefins such as ethylene, propylene and butene, liquid hydrocarbons usedas a gasoline fuel, etc. have been usually produced from petroleum. Inaddition, part of the liquid hydrocarbons has been produced by theFisher-Tropsch process. In recent years, conversion of synthesis gasinto hydrocarbons has received increasing attention because ofexhaustion of petroleum in the future. However, conventional catalystsfor use in the Fisher-Tropsch process have disadvantages in that a widevariety of hydrocarbons are produced, i.e., its distribution is toobroad, and in that n-paraffins are mainly produced and the amounts ofolefins and aromatic compounds are small.

Various modified techniques have recently been developed to producehydrocarbons from synthesis gas. For example, a process for producinghydrocarbons from synthesis gas by the use of a catalyst comprisingZSM-5 type zeolite and a metal or metal compound having an ability toreduce carbon monoxide (see Japanese Patent Application Laid-Open No.142502/1975), a process for conversion of synthesis gas usingcrystalline ferrosilicate (see Japanese Patent Application Laid-Open No.96719/1981), a process for conversion of synthesis gas using a catalystcomprising any one of ruthenium, rhodium and osmium, and ZSM-5 zeolite(see U.S. Pat. No. 4,157,338), a process for conversion of synthesis gasusing a mixture of a catalyst composed mainly of chromium and zinc and acrystalline gallosilicate catalyst (see Japanese Patent ApplicationLaid-Open No. 16427/1981), and a process for producing hydrocarbons byonce converting synthesis gas into alcohols and then the alcohols intothe hydrocarbons (see Japanese Patent Application Laid-Open No.151786/1981) are known. These processes, however, are not yetsatisfactory in that expensive raw materials are required in thepreparation of the catalysts and the yields and types of hydrocarbonsformed are not sufficiently satisfactory.

As a result of extensive investigations to develop a process forproducing useful hydrocarbons from synthesis gas in a simplified mannerand in high conversions over long periods of time, it has been foundthat the object is attained by using a catalyst comprising the abovedescribed crystalline aluminosilicate (ISI-6) and a specific metal ormetal compound.

Invention (4) is concerned with a process for producing hydrocarbonsfrom synthesis gas in the presence of a catalyst, which is characterizedin that the catalyst comprises (A) a metal or metal compound having anability to reduce carbon monoxide and (B) crystalline aluminosilicatehaving a composition, as determined after being calcined in air at 550°C. and expressed in molar ratio, represented by the formula (I) andhaving a principal X-ray diffraction pattern shown in Table 1.

The catalyst used in the process of Invention (4) comprises the abovedescribed components (A) and (B). As the component (A), metal or metalcompound having an ability to reduce carbon monoxide, various compoundscan be used. Metals which can be used inclue transition metals, i.e.,the metals belonging to Groups IB, IIB, IIIB, IVB, VB, VIB, VIIB andVIII of the Periodic Table. These metals can be used singly or incombination with each other. Suitable examples are iron, nickel, cobalt,chromium, copper, and zinc. Particularly preferred are iron, nickel andcobalt. Metal compounds which can be used include the oxides, carbides,and nitrides of the above described metals, and reduced iron. Thesemetals or metal compounds can be used appropriately. Furthermore, theycan be used in combination with other compounds. In addition, as thecomponent (A), the known catalysts, such as a Fisher-Tropsch catalyst, acatalyst for use in preparation of methanol, and a catalyst for use inpreparation of higher alcohols, can be used. Suitable examples arenickel or cobalt-base catalysts, such as Ni--MnO--Al₂ O₃ --diatomaceousearth and Co--ThO₂ --MgO--diatomaceous earth, iron-base catalysts, suchas Fe--K₂ O--Al₂ O₃, and CuO--ZnO, ZnO--Cr₂ O₃ --CuO, ZnO--Cr₂ O₃, andK₂ O--Cu--ZnO--Cr₂ O₃.

The component (B) of the catalyst for use in the process of Invention(4) is crystalline aluminosilicate (ISI-6). This crystallinealuminosilicate may contain alkali metals, such as sodium, potassium andlithium, and alkaline earth metals, such as calcium and magnesium, andcan be used also as H type silicate. The aluminosilicate can be usedalso as metal ion (for example, Pt, Pd, Ni) exchange type silicate whichis prepared by ion exchanging alkali metals or alkaline earth metalscontained therein by various techniques. A particularly suitable exampleis crystalline aluminosilicate having an X-ray diffraction pattern shownin Table 2.

The ratio of component (A) to component (B) is not critical and can bedetermined appropriately depending on the type of each component, thetype of hydrocarbon to be produced, the reaction conditions, etc. Theweight ratio of component (A) to component (B) is usually from 0.001 to0.99, preferably from 0.01 to 0.8. The components (A) and (B) can bemixed in various manners; for example, they are pelletized and thenmixed, or they are powdered and mixed in the form of powder and,thereafter, pelletized, or crystalline aluminosilicate, component (B),is impregnated with a solution of the metal compound, component (A), todeposit the component (A) on the component (B).

In the process of Invention (4), synthesis gas, i.e., a mixture ofcarbon monoxide and hydrogen, is contacted with the above preparedcatalyst to produce hydrocarbons with high efficiency. Usually, thesynthesis gas is brought into contact with the catalyst at a temperatureof 150° to 500° C., preferably 200° to 400° C. under a pressure of 0 to150 kilograms per square centimeter (gauge), preferably 10 to 100kilograms per square centimeter (gauge) at a weight hourly spacevelocity (WHSV) of 0.1 to 50 per hour, preferably 0.3 to 15 per hour.This contact reaction can be carried out by a batch process. Usually,however, it is preferably performed by a flow process. The process ofInvention (4) produces advantages in that the reaction proceedsefficiently under relatively mild conditions, the conversion ofsynthesis gas is high, and in that the yield of hydrocarbons,particularly C₅ + hydrocarbons is high.

The following examples are given to illustrate the present invention ingreater detail.

EXAMPLE 1 Solution A

Aluminum sulfate (18 hydrate): 7.52 grams

Concentrated sulfuric acid (97%): 17.6 grams

Water: 100 milliliters

Solution B

Water glass (SiO₂ : 29.0% by weight; Na₂ O; 9.4% by weight; water: 61.6%by weight): 211.0 grams

Water: 96 milliliters

Solution C

Water: 50 milliliters

Solution D

Pyridine: 188 milliliters

Ethylene glycol: 188 milliliters

Solutions A and B were gradually added dropwise at the same time toSolution C and mixed and, thereafter, the resulting mixture was adjustedto pH 8.5 by adding 13 grams of sulfuric acid (50%). Then, Solution Dwas added to the mixture, and the ratios of the components were asfollows:

silica/alumina=90 (by mole)

pyridine/silica=2.3 (by mole)

ethylene glycol/silica=3.3 (by mole)

hydroxyl ion/silica=0.09 (by mole)

The above prepared mixture was transferred to a 1-liter autoclave andreacted with stirring at 170° C. under autogenous-pressure for 20 hours.

The reaction mixture was cooled and then washed five times with 1.5liters of water. Then the mixture was filtered to separate solids, andthe solids were dried at 120° C. for 60 hours to obtain 57.0 grams ofcrystalline silicate (ISI-6) of 100% purity. An X-ray diffractionpattern of the product is shown in FIG. 1. The composition of theproduct, as determined after being calcined in air at 550° C., was0.86Na₂ O.Al₂ O₃.71.4SiO₂.

EXAMPLE 2

The procedure of Example 1 was repeated wherein the formulation ofSolution D was changed as follows:

Solution D

Pyridine: 188 milliliters

Monoethanolamine: 188 milliliters

The ratios of the components were as follows:

silica/alumina=90 (by mole)

pyridine/silica=2.3 (by mole)

monoethanolamine/silica=3.1 (by mole)

In this way, 56.2 grams of crystalline aluminosilicate (ISI-6) of 100%purity was obtained. The composition of the crystalline aluminosilicate,as determined in the same manner as in Example 1, was 0.31Na₂ O.Al₂O₃.73.1SiO₂.

EXAMPLE 3

The procedure of Example 1 was repeated wherein the formulation ofSolution D was changed as follows:

Solution D

Pyridine: 188 milliliters

Morpholine: 188 milliliters

The ratios of the components were as follows:

silica/alumina=90 (by mole)

pyridine/silica=2.3 (by mole)

morpholine/silica=2.1 (by mole)

In this way, 58.2 grams of crystalline aluminosilicate (ISI-6) of 100%purity was obtained. The composition of the aluminosilicate, asdetermined in the same manner as in Example 1, was 0.72Na₂ O.Al₂O₃.70.5SiO₂.

EXAMPLE 4

The procedure of Example 1 was repeated wherein the formulation ofSolution D was changed as follows:

Solution D

Pyridine: 188 milliliters

n-Propanol: 188 milliliters

The ratios of the components were as follows:

silica/alumina=90 (by mole)

pyridine/silica=2.3 (by mole)

n-propanol/silica=2.5 (by mole)

In this way, 58.1 grams of crystalline aluminosilicate (ISI-6) of 85%purity was obtained. It contained 15% of an impurity, crystallinesilicate of different crystal structure. The composition of thealuminosilicate, as determined in the same manner as in Example 1, was1.01Na₂ O.Al₂ O₃.68.0SiO₂.

EXAMPLE 5

The procedure of Example 1 was repeated wherein the formulation ofSolution D was changed as follows:

Solution D

Pyridine: 188 milliliters

Ethylenediamine: 188 milliliters

The ratios of the components were as follows:

silica/alumina=90 (by mole)

pyridine/silica=2.3 (by mole)

ethylenediamine/silica=2.7 (by mole)

In this way, 57.5 grams of crystalline aluminosilicate (ISI-6) of 100%purity was obtained. The composition of the aluminosilicate, asdetermined in the same manner as in Example 1, was 0.33Na₂ O.Al₂O₃.72.1SiO₂.

EXAMPLE 6

The procedure of Example 1 was repeated wherein the formulation ofSolution A was changed as follows:

Solution A

Aluminum sulfate (18 hydrate): 33.8 grams

Concentrated sulfuric acid (97%): 2.0 grams

Water: 100 milliliters

The ratios of the components were as follows:

silica/alumina=20 (by mole)

pyridine/silica=2.3 (by mole)

ethylene glycol/silica=3.3 (by mole)

In this way, 65.5 grams of crystalline aluminosilicate (ISI-6) of 100%purity was obtained. The composition of the aluminosilicate, asdetermined in the same manner as in Example 1, was 0.56Na₂ O.Al₂O₃.19.2SiO₂.

EXAMPLE 7

The procedure of Example 1 was repeated wherein the formulation ofSolution A was changed as follows:

Solution A

Aluminum sulfate: 3.37 grams

Concentrated sulfuric acid (97%): 17.6 grams

Water: 100 milliliters

The ratios of the components were as follows:

silica/alumina=200 (by mole)

pyridine/silica=2.3 (by mole)

ethylene glycol/silica=3.3 (by mole)

In this way, 55.8 grams of crystalline aluminosilicate (ISI-6) of 100%purity was obtained. The composition of the aluminosilicate, asdetermined in the same manner as in Example 1, was 1.13Na₂ O.Al₂O₃.156.1SiO₂.

EXAMPLE 8

The procedure of Example 1 was repeated wherein the formulation ofSolution D was changed as follows:

Solution D

Pyridine: 8.1 milliliters

Ethylene glycol: 5.7 milliliters

The ratios of the components were as follows:

silica/alumina=90 (by mole)

pyridine/silica=0.1 (by mole)

ethylene glycol/silica=0.1 (by mole)

In this way, 57.6 grams of crystalline aluminosilicates (ISI-6) of about90% purity was obtained. It contained small amounts of cristobalite andamorphous substances. The composition of the aluminosilicate, asdetermined in the same manner as in Example 1, was 0.96Na₂ O.Al₂O₃.68.5SiO₂.

EXAMPLE 9

The procedure of Example 1 was repeated wherein the formulation ofSolution D was changed as follows:

Solution D

Pyridinium chloride: 11.6 grams

Ethylene glycol: 47 milliliters

The ratios of the components were as follows:

silica/alumina=90 (by mole)

pyridium chloride/silica=0.1 (by mole)

ethylene glycol/silica=0.1 (by mole)

In this way, 59.5 grams of crystalline aluminosilicate (ISI-6) of about90% purity was obtained. It contained 10% of amorphous substances. Thecomposition of the aluminosilicate, as determined in the same manner asin Example 1, was 0.92Na₂ O.Al₂ O₃.70.3SiO₂.

EXAMPLE 10

The procedure of Example 1 was repeated wherein the formulation ofSolution A was changed as follows:

Solution A

Aluminum sulfate: 1.35 grams

Concentrated sulfuric acid (97%): 17.6 grams

Water: 100 milliliters

The ratios of the components were as follows:

silica/alumina=500 (by mole)

pyridine/silica=2.3 (by mole)

ethylene glycol/silica=3.3 (by mole)

In this way, 58.0 grams of crystalline aluminosilicate (ISI-6) of about80% purity was obtained. It contained 20% of other zeolites.

COMPARATIVE EXAMPLE 1

The procedure of Example 1 was repeated wherein the formulation ofSolution D was changed as follows:

Solution D

Ethylene glycol: 188 milliliters

The ratios of the components were as follows:

silica/alumina=90 (by mole)

ethylene glycol/silica=3.3 (by mole)

In this case, however, the desired crystalline aluminosilicate was notobtained at all, and 56.0 grams of other crystalline aluminosilicate(ISI-4) of 100% purity was obtained.

EXAMPLE 11

A mixture of crystalline aluminosilicate (ISI-6) as obtained in Example1 and alumina sol was extrusion molded, and calcined in air at 550° C.for 6 hours. The mold (alumina content: 35% by weight) (2.5 grams) wascharged to a flow type reactor through which methanol was passed. Inthis way, methanol was contacted with the crystalline aluminosilicate(ISI-6) at 370° C. under atmospheric pressure at a weight hourly spacevelocity (WHSV) of 2.2 per hour. The results are shown in Table 3.

COMPARATIVE EXAMPLE 2

Crystalline aluminosilicate zeolite ZSM-34 (prepared by the method ofExample 1 in Japanese Patent Application Laid-Open No. 58499/1978) (2.5grams) was charged to a flow type reactor through which methanol waspassed. In this way, methanol was contacted with the crystallinealuminosilicate zeolite ZSM-34 at 371.1° C. under atmospheric pressureat a weight hourly space velocity (WHSV) of 3.0 per hour. The resultsare shown in Table 3.

EXAMPLE 12

Crystalline aluminosilicate (ISI-6) as obtained in Example 1 wascalcined in air at 550° C., and then was ion-exchanged twice at roomtemperature with 1 normal ammonium nitrate. The amount of ammoniumnitrate used herein was 5 milliliters per 1 gram of the crystallinealuminosilicate. After ion-exchange was completed, the obtained ammoniumtype crystalline aluminosilicate was washed with pure water, dried at120° C. for 6 hours, and then calcined in air at 550° C. for 6 hours toobtain proton type (H type) crystalline aluminosilicate.

A molton iron catalyst (catalyst for synthesis of ammonia, produced byBASF Co., S6-10RED) (1.25 grams) was mixed with 1.25 grams of H typecrystalline aluminosilicate (ISI-6) mold powder as prepared above. Thethus prepared mixed catalyst was charged to a flow type reaction tube,reduced with hydrogen at 450° C. under atmospheric pressure for 14hours, and then activated with synthesis gas (molar ratio of hydrogen tocarbon monoxide=2:1) at 250° C. under atmospheric pressure at a weighthourly space velocity (WHSV) of 0.49 per hour for 2 hours. Then, thesynthesis gas (molar ratio of hydrogen to carbon monoxide=2:1) waspassed therethrough and contacted with the mixed catalyst at 330° C.under a pressure of 20 kilograms per square centimeter (gauge) at aweight hourly space velocity (WHSV) of 1.46 per hour. The results areshown in Table 4.

                  TABLE 3                                                         ______________________________________                                                               Comparative                                                           Example 11                                                                            Example 2                                              ______________________________________                                        Conversion of Methanol (%)                                                                     93.1      85.9                                               Hydrocarbon Composition                                                       (% by weight)                                                                 C.sub.1           3.3       2.3                                               C.sub.2 (Olefin Content)                                                                       16.7 (16.5)                                                                             25.9 (25.9)                                        C.sub.3 (Olefin Content)                                                                       13.2 (11.6)                                                                             19.7 (17.6)                                        C.sub.4 (Olefin Content)                                                                       29.2 (22.5)                                                                              7.3 (5.4)                                         C.sub.5.sup.+    37.7      45.1                                               Olefin Selectivity (%)                                                                         50.6      48.9                                               ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                                            Example 12                                                ______________________________________                                        Conversion of Carbon Monoxide (%)                                                                   98.8                                                    Hydrocarbon Composition (%)                                                   C.sub.1               16.8                                                    C.sub.2               11.8                                                    C.sub.3               15.1                                                    C.sub.4               13.1                                                    C.sub.5.sup.+         43.1                                                    ______________________________________                                    

What is claimed is:
 1. A process for preparing a crystallinealuminosilicate which has a composition represented by the generalformula after being calcined in air at 500° C. as follows:

    pM.sub.2/n O.Al.sub.2 O.sub.3.qSiO.sub.2

wherein M represents at least one element selected from hydrogen, alkalimetals, and alkaline earth metals, n represents the valence of M, and pand q each represent a molar ratio and are chosen within the ranges of0.5≦p≦3.0 and 5≦q≦500, and has the X-ray diffraction patern set forth inTable 2 which comprises reacting an aqueous mixture containing (a) asilica source, (b) an alumina source, (c) an alkali metal and/oralkaline earth metal source, (d) at least one pyridine compound selectedfrom the group consisting of pyridine, pyridinium chloride,methylpyridine, dimethylpyridine, ethylpyridine, trimethylpyridine andethylmethylpyridine, and (e) at least one compound selected from thegroup consisting of methanol, ethanol, propanol, n-butanol, isopropanol,ethylene glycol, propylene glycol, dimethyl ether, diethyl ether,isopropylamine, morpholine, ethylenediamine, propylenediamine,phenylenediamine, monoethanolamine, monopropanolamine anddiethanolamine, in the following ratios: silica (SiO₂)/alumina (Al₂O₃)≧5 pyridine compound/silica=0.01 to 100 component (e)/silica=0.01 to100 hydroxyl ion/silica=0.001 to 0.5 (excluding hydroxyl ions resultingfrom organic bases) water/silica=5 to 1,000 alkali metal and/or alkalineearth metal/silica=0.01 to 3at a temperature ranging between 100° and300° C. till the crystalline aluminosilicate is formed.